LEAVENING AGENTS

Abstract

A leavening composition which gives an enhanced leavening and reduced use of acidulants comprises (1) an alkali metal bicarbonate, (2) at least 0.1 and preferably at least mole per mole of bicarbonate of a precipitant which is a water-soluble alkaline earth metal salt, and (3) optionally an acidulant, wherein (2) and (3) are present in a total amount from 105 to 800% of the stoichiometric amount that would be required to react fully with (1) in a boiling aqueous solution. In a preferred embodiment the acidulant forms a water insoluble calcium or magnesium salt and is sufficient to provide more than 0.105 g replaceable hydrogen per 100 mmol bicarbonate, and the precipitant is a water soluble calcium or magnesium salt which is capable of precipitating or complexing with said acidulant and is present in an amount sufficient to provide a final pH below 6.5 when the leavening agent is heated in a bakery mix, which allows the inclusion of an effective amount of a preservative.

Claims

1. A leavening agent comprising: (1) An alkali metal or ammonium bicarbonate; (2) At least 0.1 and preferably at least 1 mole per mole of bicarbonate of Precipitant optionally comprising a Precipitating Acidulant; and (3) Optionally an Acidulant; wherein (2) and (3) are present in a total amount from 105 to 800% of the stoichiometric amount that would be required to react fully with (1) in a boiling aqueous solution.

2. A leavening agent comprising: (1) Alkali metal bicarbonate; (2) A Precipitant and/or Precipitating Acidulant, in a total proportion sufficient to provide from 1 to 8.8 g, and preferably at least 1.1 g, Precipitating Cation per 100 mmol bicarbonate; and (3) An Acidulant, which may be or may comprise said Precipitating Acidulant, in a total proportion sufficient to provide from 0.025 to 0.2 g Replaceable Hydrogen per 100 mmol of bicarbonate.

3. A leavening agent comprising as components: (1) An alkali metal bicarbonate; (2) A Precipitant; and; (3) Optionally an Acidulant; wherein y>x+5 between x=0 and x=47.5, and between x=52.5 and 105; and y>80 between x=47.5 and x=52.5; where x is the amount of sodium bicarbonate mmols per 100 mmols of the said components that would remain after complete reaction with any non-phosphate Acidulants present and y is the amount of Precipitant in mmols per 100 mmols of the said components.

4. A leavening agent comprising: (1) Alkali metal bicarbonate; (2) A Precipitant and/or Precipitating Acidulant, in a total proportion sufficient to provide c=from 25 to 200; and (3) An Acidulant, which may be or may comprise said Precipitating Acidulant, in a total proportion sufficient to provide h=from 25 to 200, and preferably h+2c>100; where c is the total mmol Precipitating Cation per 100 mmol bicarbonate and h is the total mmol hydrogen ion per 100 mmol bicarbonate.

5. A leavening agent according to claim 1 comprising: (1) Alkali metal bicarbonate; (2) An Acidulant that forms a non-Water-Soluble calcium or magnesium salt sufficient to provide more than 0.105 g Replaceable Hydrogen per 100 mmol bicarbonate; (3) A Precipitant that is a water soluble salt of an alkaline earth metal capable of precipitating or complexing with said Acidulant with an acid that is stronger than said Acidulant in an amount sufficient to provide a final pH below 6.5 when the leavening agent is heated in a bakery mix; (4) An effective amount of a preservative.

6. A leavening agent according to claim 1 comprising: (1) Alkali metal bicarbonate; an Acidulant that forms a water insoluble calcium or magnesium salt sufficient to provide more than 105 mmols replaceable hydrogen per 100 mmols bicarbonate; (2) A Precipitant that is a water soluble salt of an alkaline earth metal capable of precipitating said Acidulant with an acid which is stronger than said Acidulant in an amount sufficient to provide a final pH below 6.5 when the leavening agent is heated in a bakery mix; and (3) An effective amount of a preservative.

7. A leavening agent according to any claim 1 wherein the alkali metal bicarbonate is sodium and/or potassium bicarbonate.

8. A leavening agent according to claim 1 wherein the alkaline earth metal is calcium and/or magnesium.

9. A leavening agent according to claim 1 wherein the Precipitant is a salt of formic, acetic, fumaric, lactic, aconitic, itaconic, citraconic, tartaric, adipic, ascorbic, malic, lactobionic, hydrochloric and/or sulphuric acid.

10. A leavening agent according to claim 1 wherein the Precipitant is calcium chloride.

11. A leavening agent according to claim 1 wherein the acidulant comprises phosphorus oxyacids and/or their mono-, di- and/or tri-basic salts such as SALP, SAPP, phosphoric acid, mono- and/or di-sodium and/or potassium phosphates, mono- and/or di-calcium phosphate and/or organic acids and/or their acid salts such as MSC, glucono-delta-lactone, fumaric acid, maleic acid, malic acid, succinic acid, adipic acid, tartaric acid, mono sodium tartrate, citraconic acid, aconitic acid, itaconic acid, mono potassium citrate and/or tartrate, hydrolysed lactones and/or polylactic acid and/or sodium aluminium sulphate

12. A leavening agent according to claim 5 wherein the preservative is selected from sorbic acid, potassium sorbate, sodium sorbate, calcium sorbate, sulphur dioxide, sodium sulphite, sodium bisulphite, sodium metabisulphite, potassium sulphite, potassium metabisulphite, potassium hydrogen sulphite, calcium sulphite, calcium hydrogen sulphite, propionic acid, sodium propionate, potassium propionate and/or calcium propionate.

13. A baking powder comprising a leavening agent according to claim 1.

14. A self-raising flour comprising a leavening agent according to claim 1.

15. A bakery mix comprising a leavening agent according to to claim 1.

16. The use in baking of a leavening agent according to to claim 1.

17. A method of baking comprising heating a bakery mix as claimed in claim 15.

18. A confection prepared by baking a bakery mix as claimed in claim 15.

19. A leavening agent comprising: (i) An alkali metal or ammonium bicarbonate; (ii) Optionally an Acidulant selected from phosphorus oxyacids and their mono-, di- and tri-basic salts, including SALP, SAPP, phosphoric acid, mono- and di-sodium and potassium phosphates, and mono- and di-calcium phosphate, and MSC, glucono-delta-lactone, fumaric acid, maleic acid, malic acid, succinic acid, adipic acid, tartaric acid, monosodium tartrate, citraconic acid, aconitic acid, itaconic acid, mono potassium citrate and tartrate, hydrolysed lactones and polylactic acid and sodium aluminium sulphate and mixtures thereof in an amount from 0 to 90% of the stoichiometric amount required to react with the bicarbonate and (iii) A Precipitant; and wherein (ii) and (iii) are present in a total amount from 110 to 250% of the stoichiometric amount that would be required to react fully with (i) in a boiling aqueous solution.

20. A leavening agent comprising: (1) An alkali metal bicarbonate; (2) An Acidulant in a proportion of from 90 to 110% of the stoichiometric amount based on the bicarbonate; and (3) A Precipitant in a total proportion of from 28 to 120 mmol per 100 mmol bicarbonate.

21. A pancake batter comprising: flour, at least 30% by weight of water and a viscosifier comprising from 0.001 to 10% by weight, based on the weight of the batter, of a water soluble calcium or magnesium salt.

22. A method of making pancakes which comprises frying a batter according to claim 21.

23. Pancakes made by the method of claim 22.

Description

EXAMPLE 1

[0185] Bakery trials with sodium bicarbonate and Precipitant, in the stoichiometric amount required to precipitate the carbonate formed by thermal decomposition of the bicarbonate in aqueous solution, as in the balanced system described by Wu (vs), had shown wide variations in pH, which was undesirably high giving a dark crumb and bitter aftertaste. To compensate for the expected 50% reduction in CO.sub.2 available from the thermal decomposition compared with conventional acid/base leavening systems, the amount of bicarbonate was proportionately increased. None of the tests gave a commercially viable product.

[0186] An Acidulant-free composition according to the invention comprising a substantial excess of Precipitant over the stoichiometric amount, and using conventional levels of addition of bicarbonate was compared to one of the earlier formulations, and also with sodium bicarbonate alone at both the conventional and increased levels and calcium chloride alone, in the following Madeira cake recipe.

TABLE-US-00001 Heat treated cake flour 300 Caster sugar 391.8 Skimmed milk powder 22.2 Salt 7.5 Sweetener 211.2 Skimmed milk 19.6 Water 177.9

[0187] The comparison consisted of 8.9 g sodium bicarbonate and 5.9 g calcium chloride. The example consisted of 5.11 g sodium bicarbonate and 5.9% calcium chloride. The results are shown in the following table I:

TABLE-US-00002 TABLE I pH Volume (cm.sup.3) Colour Comparison 8.6 1152 Light brown Example 1 8.4 1183 Off white 8.9% soda 9.2 1012 Brown 5.11% soda 8.8 968 Dark brown 5.9% 6.3 952 White

[0188] The product of the invention although using substantially less bicarbonate than the control provided a greater increase in volume, lower pH and almost no discolouration.

EXAMPLES 2-4

[0189] Four formulations were prepared using mixtures of Precipitant and Acidulant at various levels and compared with a commercial product in bakery trials, using the following recipe.

[0190] A scone mix was prepared with the composition, based on weight of flour:

TABLE-US-00003 Plain flour 100 Baking powder 10.3 Caster sugar 20 Unsalted butter 30 Milk 50

[0191] The pH of the scones was noted. The results are set out in the following table II, in which all proportions are in grams.

TABLE-US-00004 TABLE II Example NaHCO.sub.3 flour CaCl.sub.2 MCPa SAPP pH Comparative 0.74 0.4 0 0 1.04 7.3 2 1.14 0.24 0.495 0.47 0 8.8 3 0.765 0.24 0.47 0.495 0 7.35 4 0.64 0.27 0.62 0.35 0 7.9 5 0.39 0.24 0.78 0.2 0 6.7

EXAMPLE 6-8

[0192] Three leavening formulations according to the invention were tested in the following Madeira cake recipe of Example 1. The pH was acceptable in all cases and the examples had a brighter crumb than the control, which used a balanced Acidulant/soda system. The height in mm was measured in the centre and edge. No sagging was observed in the middle. The improved rise compared to the control resulted from a late surge in gas evolution. The results are set out in the following table in which proportions are percent by weight based on total weight.

TABLE-US-00005 TABLE III Control 6 7 8 Wheat flour 18.5 0 0 0 CaCl.sub.2 0 29.8 14.5 11.9 Calcium formate 0 0 17.0 13.9 MCPa 0 27.2 26.5 0 NaHCO.sub.3 34.4 43.1 42 34.3 SAPP 47.1 0 0 0 GDL.sup.1 0 0 0 39.3 Height (mid) 74.07 86.43 89.03 91.46 Height (edge) 68.22 60.97 59.58 63.91 pH 7.7 7.8 7.7 8.2

EXAMPLES 9 and 10

[0193] Two phosphate-free baking powders according to the invention were prepared using fumaric acid as Acidulant. The two examples were used with a Madeira cake recipe in baking trials and compared with a commercial formulation. The results are set out in the following table IV, in which all proportions are in grams, and heights are in mm.

TABLE-US-00006 TABLE IV CONTROL 9 10 Wheat flour 3.6 0 0 SAPP 9.39 0 0 CaCl.sub.2 0 5.96 9.68 NaHCO.sub.3 6.81 12.78 12.78 Fumaric acid 0 6.64 6.64 Total weight 19.8 25.4 29.1 Height (middle) 87.83 91.38 93.27 Height (edge) 62.67 62.47 59.28 pH 7.2 7.4 7.5 Taste sweet sweet sweet Aftertaste pyrophosphate clean CaCl.sub.2

EXAMPLES 11-14

[0194] Four formulations with calcium formate as the sole Precipitant were prepared and tested in the scone recipe of example II. The pH of the scones was determined. The results are set out in the following table V.

TABLE-US-00007 TABLE V Ca MCPa NaHCO MCP m formate pH 11 26.36 42.91 0 30.72 7.1 12 0 42.49 27.09 30.42 7.3 13 22.22 41.32 0 36.46 7.9 14 23.86 44.37 0 31.77 8.3

EXAMPLES 15-20

[0195] Six leavening formulations were prepared according to the invention, using a system comprising fumaric acid, sodium bicarbonate and various mixtures of calcium and magnesium chlorides. The formulations were used in the bakery mix of Example I and compared with a sample with only magnesium. The pH of the scones was noted. The results are set out in the following table VI, in which all proportions are in grams

TABLE-US-00008 TABLE VI CaCl.sub.2:MgCl Fumaric Soda CaCl.sub.2 MgCl.sub.2 pH 100:0 26.15 50.35 23.50 0.00 7.48 80:20 26.33 50.70 18.92 4.06 7.59 60:40 26.50 51.03 14.29 8.18 7.45 40:60 26.68 51.37 9.61 12.34 7.62 20:80 26.86 51.72 4.84 16.57 7.64 10:90 26.96 51.91 2.42 18.70 7.41 0:100 27.05 52.09 0.00 20.85 8.02

[0196] It will be seen that magnesium chloride alone gave a relatively high pH, but that the addition of even small amounts of calcium chloride significantly lowered the pH of the product.

EXAMPLES 21-22

[0197] Two phosphate-free baking powders according to the invention were prepared using fumaric acid as an Acidulant with calcium formate and calcium chloride respectively. They were compared with two SAPP based baking powders and two fumaric based baking powders using Acidulant only, in a standard Madeira cake recipe. The SAPP and pure fumaric based baking powders were used at two different addition levels. The lower addition level in baking trials and compared with a commercial formulation. The results are set out in the following table VII, in which all proportions are in percent by weight based on the weight of flour, and heights are in mm.

TABLE-US-00009 TABLE VII (SAPP) (SAPP) 21 Fumaric Fumaric 22 SAPP 2.348 3.03 CaCl.sub.2 1.0325 Calcium 1.210 formate NaHCO.sub.3 1.703 2.213 2.213 1.703 2.213 2.213 Fumaric 1.150 1.175 1.526 1.150 acid Height 75.65 79.14 89.81 78.16 85.68 90.22 (middle) Height 67.78 67.81 62.23 63.23 62.99 61.94 (edge) pH 7.5 7.8 7.7 6.9 6.9 7.4 Taste Clean Slight Clean Slightly Slightly Clean chemical astringent astringent Crumb Open and Very open Tight Liquor Liquor Tight uneven and uneven soft. logged logged but soft.

EXAMPLE 23

[0198] A solution of 0.821 g anhydrous mono calcium phosphate in 250 ml deionised water at 90 was titrated with 0.5M sodium hydroxide solution and the pH plotted against volume of added titrant. The first inflexion occurred at 6.5 ml corresponding to a Neutralisation Value of 37. A second inflexion was observed at 13 ml corresponding to a Neutralisation Value of 79.

[0199] The experiment was repeated in the presence of 3.5 g calcium chloride. A single inflexion was observed at 20.5 ml corresponding to a Neutralisation Value of 125.

[0200] Similar titrations against monosodium phosphate gave a first inflexion corresponding to a Neutralisation Value of 68, in the absence of calcium chloride, and 139.5, with added calcium chloride. Thus addition of calcium chloride greatly increases the neutralisation value of both mono calcium and mono sodium phosphates. Similar titrations against fumaric acid showed no such change in the Neutralisation Value

EXAMPLE 24

[0201] 40 g of mini scone dough was prepared and baked using dipotassium phosphate, CaCl.sub.2) and sodium bicarbonate. The recipe was: [0202] 57 g plain flour [0203] 5 g skimmed milk powder [0204] 1 g salt [0205] 5 g vegetable oil [0206] 35 g water [0207] 0.75 g sodium bicarbonate [0208] 1.72 g dipotassium phosphate [0209] 1.1 g CaCl.sub.2)

[0210] The pH of a 1% solution of dipotassium phosphate was measured to be 9.3 at 25 C. The mini scone dough was baked at 225 C. for 13 minutes. The scones appeared light and fluffy.

[0211] The scones were left to cool, were crumbed in to a 250 ml beaker, mixed with 70 ml of deionised water and covered with Clingfilm. After 30 minutes a slurry was made out of the water/scone mixture by mixing with a spatula for 2 minutes. The pH of the slurry was found to be 7.7 using a pH electrode.

EXAMPLE 25

[0212] Four trial batches of mini-scones were prepared using leavening systems comprising sodium bicarbonate with, respectively, stoichiometric SAPP, 10% excess SAPP, 50% excess SAPP and 10% excess SAPP with calcium chloride. The pH of the scones was measured.

TABLE-US-00010 TABLE VIII SAPP Stoichiometric 10% excess 50% excess 10% excess + CaCl.sub.2 pH 7.5 7.25 6.8 6.3

[0213] Thus even a 50% excess of SAPP (an unrealistically high concentration) could not reduce the pH to 6.5, at which most preservatives begin to be reasonably effective. However, in the presence of calcium chloride a pH of 6.3 was obtained using only 10% excess SAPP.

EXAMPLE 26

[0214] MSC is not an effective acidulant, when used in a stoichiometric proportion with sodium bicarbonate. Two Madeira cakes were prepared using as leavening system 7.665 g sodium bicarbonate with, respectively, stoichiometric MSC (9.768 g) and 75% stoichiometric MSC (7.335 g) plus 4.78 g CaCl.sub.2.

[0215] The MSC alone did not generate sufficient CO.sub.2 during the bake and the cake failed to rise. The MSC and Precipitant showed little evidence of rising during the early stages of heating but rose rapidly when the temperature passed 60 C., to give alight well leavened texture.

EXAMPLES 27-28

[0216] Four leavening systems were prepared using, respectively, MSC and citric acid with and without CaCl.sub.2). The systems were tested in a Madeira cake formulation.

TABLE-US-00011 TABLE IX Example Example Ingredients: 27 Comparison 28 Comparison Soda (g) 7.665 7.665 10.541 10.541 CaCl.sub.2 (g) 4.78 4.780 MSC (g) 7.335 9.768 Citric (g) 6.58 8.04 Total Leavening (g) 19.78 17.43 21.90 18.58

[0217] The bake loss, average shoulder height, middle cake height and crumb pH was determined.

TABLE-US-00012 TABLE X Average Height Average Average in Shoulder Bake Leavening middle (mm) Height (mm) Loss pH MSC + CaCl.sub.2 81.62 63.03 7.72% 7.88 MSC 64.45 68.76 7.33% 7.09 Citric + CaCl.sub.2 74.57 61.04 7.26% 8.36 Citric 59.70 60.94 6.90% 7.43

[0218] The trials containing CaCl.sub.2) produced much better Madeira cakes compared to the trials that did not contain any precipitant. The trials using MSC as the acidulant produced better cakes than the trials that used citric acid with or without CaCl.sub.2) precipitant Liquor logging was an issue for both trials using citric acid. Trials containing CaCl.sub.2) had higher pH compared to trials that did not.

EXAMPLES 29-40

[0219] To illustrate the extent to which it is possible to reduce pH using a precipitant, and the extent to which it is possible to reduce the Acidulant without obtaining products with a higher pH than the control, mini scone tests were carried out with two commercial SALP products. Series A and B used SALP sold respectively under the registered trademarks LEVEN LITE and BUDAL 2308. In each case the control used a stoichiometric amount of SALP and the examples included a small excess of calcium chloride. The proportion of Acidulant was progressively reduced, until the pH of the scones matched that of the control. In addition, in series A, the effect of replacing the Precipitant with an equivalent amount of hydrochloric acid was noted. In this test 35 ml of 0.1018M hydrochloric acid solution was added. The results were as follows:

TABLE-US-00013 TABLE XI SALP Soda CaCl.sub.2 Example Reduction (g) (g) (g) HCl pH A Control 0% 0.75 50.7 7.5 29 0% 0.75 0.75 1 5.9 30 10% 0.68 0.75 1 6.3 31 20% 0.60 0.75 1 6.5 32 30% 0.53 0.75 1 6.9 33 40% 0.45 0.75 1 7.2 34 50% 0.38 0.75 1 7.4 HCl 50% 0.38 0.75 4.1 7.2 mmol B Control 0.75 0.75 7.3 35 0% 0.75 0.75 1 6.2 36 10% 0.68 0.75 1 6.6 37 20% 0.60 0.75 1 6.9 38 30% 0.53 0.75 1 7.2 39 40% 0.45 0.75 1 7.6 40 50% 0.38 0.75 1 7.9

[0220] In each case the examples with Precipitant gave superior leavening to the controls. The test with hydrochloric acid gave negligible leavening effect. Comparisons of reaction rates showed that the hydrochloric acid reacted rapidly with the bicarbonate on addition to dough at room temperature, the reaction being 60% complete after a few seconds. In contrast the Precipitant reacted slowly at first taking three minutes to reach about one third completion, at which point it appeared to reach an equilibrium. No further evolution of carbon dioxide was observed over the next five minutes.

EXAMPLES 41-44

[0221] Madeira cake trials were carried out comparing sodium bicarbonate with potassium bicarbonate (KBC) and MSC with citric acid.

TABLE-US-00014 TABLE XII Ingredients (g): 41 42 43 44 Soda 7.7 10.5 KBC 9.2 12.7 CaCl.sub.2 4.8 4.8 4.8 4.8 MSC 7.3 7.3 Citric 6.6 6.6 Total Leavening 19.8 21.9 21.3 24.0 (g) Height (middle) 81.6 74.6 87.4 78.0

[0222] The two trials with potassium bicarbonate were each slightly better than the corresponding trials with sodium bicarbonate. The two trials with MSC were substantially better than the two with citric acid.

EXAMPLE 45

[0223] The reaction between SAPP and bicarbonate has hitherto been assumed to involve the formation of tetra sodium pyrophosphate and carbon dioxide according to the mechanism:

2Na.sub.2H.sub.2P.sub.2O.sub.7+4NaHCO.sub.32Na.sub.4P.sub.2O.sub.7+4H.sub.2O+4CO.sub.2.

[0224] This reaction would evolve 100% of the available carbon dioxide, i.e. one mole per mole of bicarbonate. It would, however, entail a reaction between each of the available hydrogen atoms of the SAPP and a molecule of bicarbonate. The pK.sub.a for the deprotonation of the HP.sub.2O.sub.7.sup.3 ion is 9.3. This is too high for a reaction with a base as weak as bicarbonate to be credible.

[0225] We believe a more probable reaction would involve the formation of trisodium pyrophosphate, sodium carbonate and carbon dioxide:

2Na.sub.2H.sub.2P.sub.2O.sub.7+4NaHCO.sub.32Na.sub.3HP.sub.2O.sub.7+Na.sub.2CO.sub.3+3H.sub.2O+3CO.sub.2.

[0226] This reaction only releases three moles carbon dioxide for every four moles of bicarbonate, i.e. 75% of the available carbon dioxide. A subsequent cyclical reaction is possible, firstly between the trisodium pyrophosphate and the strongly basic sodium carbonate to form sodium bicarbonate and tetra sodium pyrophosphate followed by reaction between the bicarbonate and SAPP. This reaction would require an infinite number of cycles to release all the available carbon dioxide.

[0227] To determine which of these mechanisms corresponds most closely to reality and how the present invention affects the yields that can be obtained, we have carried out a series of tests at the either end of the critical temperature range, i.e. 70 C. and 90 C., using sodium bicarbonate, (i) alone, (ii) with calcium chloride, (iii) with an equivalent amount of SAPP (i.e. 0.5 mols per mol bicarbonate) and (iv) with an equivalent amount of SAPP and 0.06 mols calcium chloride per mol bicarbonate according to our invention. The test mixture was heated in aqueous solution for fifteen minutes and the proportion of the available carbon dioxide evolved was determined by the Chittick method. The results are set out in the following table:

TABLE-US-00015 TABLE XIII Temperature Leavening system pH cold % CO.sub.2 liberated 70 C. NaHCO.sub.3 8.3 24.2 70 C. NaHCO.sub.3 + CaCl.sub.2 7.5 39.4 70 C. NaHCO.sub.3 + SAPP 6.7 66.2 70 C. NaHCO.sub.3 + SAPP + CaCl.sub.2 6.2 89.3 90 C. NaHCO.sub.3 8.8 40.5 90 C. NaHCO.sub.3 + CaCl.sub.2 8.1 62.5 90 C. NaHCO.sub.3 + SAPP 8.3 78.1 90 C. NaHCO.sub.3 + SAPP + CaCl.sub.2 7.7 97.4

[0228] It will be seen that the amount of carbon dioxide evolved in the reaction between SAPP and bicarbonate does not approach the 100% of theoretical, which the currently accepted theory predicts, but approximates to the 75% predicted by our proposed mechanism.

[0229] Addition of calcium chloride, according to the present invention, results in the evolution of amounts of carbon dioxide close to 100%. This supports our theory that the second hydrogen atom of the SAPP molecule is not sufficiently active to react with bicarbonate, but is activated by the addition of a Precipitant, e.g. by precipitation of calcium pyrophosphate accompanied by release of an equivalent amount of hydrochloric acid.

EXAMPLES 46-48

[0230] To determine the effect of calcium and magnesium salts in pyrophosphate-based baking powders on the pH of cakes obtained from batter, a series of batches of celebration cakes was prepared from a batter having the following composition:

TABLE-US-00016 TABLE XIV Ingredient Weight (g) HT flour 250 Granulated sugar 210 Xanthan gum 0.50 Skimmed milk powder 15.0 Potassium sorbate 0.90 Egg 138 Water 96.0 Glycerine 13.5 Emulsifier 9.6 Unsalted butter 132 TOTAL 865.5

[0231] The following baking powder formulations were tested: [0232] A. Control:3.92 g soda (sodium bicarbonate), 5.37 g SAPP [0233] B. Control+citric acid:3.0 g soda, 4.1 g SAPP, 2.5 g citric acid [0234] C. SAPP+calcium:3.0 g soda, 4.8 g SAPP, 4 g CaCl.sub.2), 1.6 g SAPP 10 [0235] D. SAPP+magnesium:3.0 g soda, 4.8 g SAPP, 8.9 g MgSO.sub.4.7H.sub.2O, 1.6 g SAPP10 [0236] E. MCP+calcium:3.0 g soda, 3.6 g CaCl.sub.2), 3.92 g MCPa

[0237] Batches of cakes were prepared using each of the above leavening systems and the heights and pH were compared as set out in the following table.

TABLE-US-00017 TABLE XV Shoulder height (mm) Middle height(mm) pH A 36.6 54.5 7.26 B 27.4 38.3 5.81 46 36.0 53.2 5.84 47 32.2 57.7 5.93 48 29.8 42.1 5.6

[0238] The control, system (A), was a typical commercial SAPP formulation, which, when used in the normal stoichiometric proportion gives a pH far in excess of that required to allow the effective use of preservatives. For example, one of the commonest preservatives in baking, potassium sorbate, is ineffective above pH 6.5 and requires a pH of about 5.5 for optimum effectiveness.

[0239] Addition of citric acid to the control, system (B), gave a pH below 6, but at the expense of leavening, which was below commercially acceptable standards.

[0240] Addition of magnesium according to the invention (Example 45) gave a pH below 6, without significant loss of leavening, but best results were obtained using calcium according to the invention, (Example 46), which gave both a low pH and improved leavening.

[0241] MCP with calcium according to the invention (Example 47) achieved the lowest pH, very close to the optimum, but at the expense of some loss of leavening.

EXAMPLES 49 and 50

[0242] Example 1 was repeated, using for comparison two further Acidulant-free examples of the invention containing, respectively, an excess of 31% and 122% calcium chloride over the stoichiometric amount. In each case the amount of sodium bicarbonate was 5.11 g. The results are set out in Table XVI.

TABLE-US-00018 TABLE XVI Example Calcium chloride (g) pH Volume (cm.sup.3) 1 5.9 8.39 1152.2 49 4.43 8.45 1137.8 50 7.38 8.13 1124.5

[0243] All products were free from off flavours and excessive discolouration of the crumb.

EXAMPLE 51

[0244] To test the applicability of the invention in fried products, the Acidulant free leavening system of Example 1 was added to a cake donut recipe and compared with a commercial SAPP based leavening system. The control gave a product with a pH of 7.81. Despite having a pH of 8.58, the product of the invention was similar in appearance and taste to the control.

EXAMPLES 52 and 53

[0245] It was noted that in certain muffin recipes the Acidulate-free leavening system according to Example 1 of the invention gave a paler crust than usually observed with conventional acid base leavening systems and the sodium chloride formed gave the product an undesirably salty taste.

[0246] To remedy the first of these defects 10% of the sucrose in the recipe was replaced by dextrose and to avoid the salty taste the proportion of calcium chloride was reduced (example 51) and alternatively the total amount of leavening agent was reduced (Example 52). The results are set out in Table XVII with all weights in grams.

TABLE-US-00019 TABLE XVII Leavening As system Control Example 1 Example 52 Example 53 Dextrose 0 0 10 10 Caster sugar 195 195 185 185 Sweetener 150 150 150 150 Skimmed milk 12 12 12 12 powder Egg 90 90 90 90 HT flour 300 300 300 300 Water 225 225 225 225 Sodium 2.58 3.87 3.87 2.9 bicarbonate SAPP 3.53 0 0 0 Calcium 0 4.43 3.32 3.32 chloride Crust Normal Pale Normal Normal Taste Normal Salt Normal Normal Volume 482.4 cm.sup.3 499.7 cm.sup.3 466.9 cm.sup.3 452.5 pH 7.6 8.4 8.4 8.3

EXAMPLES 54-59

[0247] The pH values typifying Acidulant-free systems of the invention do not cause problems of discolouration or flavour but may need lowering to meet the requirements of some customers. Two Acidulant free systems and four examples with Acidulant were compared in a high ratio pound cake recipe the results are given in Table XVIII. The weights of the components of the leavening system are in grams per 300 grams of flour and the volumes in cubic centimetres.

TABLE-US-00020 TABLE XVIII Example Control 54 55 56 57 58 59 soda 1.37 2.06 2.25 2.25 1.64 2.25 2.25 SAPP 3.53 0 0 0 0 0 0 CaCl.sub.2 0 2.35 1.77 1.77 1.02 2.35 1.77 malic 0 0 0.63 0 0 0 0 GDL 0 0 0 1.67 0 0 0 MSC 0 0 0 0 1.57 0 0 Citric 0 0 0 0 0 0.6 0 Volume 514.8 543.3 561.0 581.2 571.6 496.3 537.3 pH 7.4 8.4 8.2 8.1 7.4 8.6 8.4

EXAMPLES 60-62

[0248] A stoichiometric mix of calcium chloride and sodium bicarbonate as used in the examples of Wu (vs) was compared with leavening agents of the invention containing progressively increased amounts of calcium chloride relative to bicarbonate in a pound cake recipe set out in table XIX.

TABLE-US-00021 TABLE XIX Weight (g) Plain flour 200 Caster sugar 200 Egg 200 Shortening 200 Sodium monophosphate 10 Leavening 6.52

[0249] The three examples comprised, respectively 125%, 150% and 175% of the stoichiometric ratio of calcium chloride to bicarbonate. The results are set out in the following table XX.

TABLE-US-00022 TABLE XX Example Comparative 60 61 62 % stoichiometric 100 125 150 175 Bicarbonate 4.13 4.13 4.13 4.13 Precipitant 2.73 3.41 4.09 4.77 Volume (cm.sup.3) 631.4 672.3 678.9 675.8 pH 8.7 8.6 8.4 8.3 Colour Dark Pale Pale Very Pale

[0250] The addition of excess Precipitant according to the invention significantly improves the leavening effect. In conventional acid/base systems excess Acidulant causes too rapid a reaction and premature loss of carbon dioxide leading to a reduction in volume.

[0251] The excess Precipitant progressively lowers the pH. This is surprising since the pH of calcium chloride in solution is 8.6.

[0252] The three examples of the invention did not exhibit the darkening effect or the bitter/soapy off flavours commonly associated with alkaline pH.

EXAMPLES 63-66

[0253] To illustrate the effect of calcium on orthophosphates, trials were conducted with the mono and di orthophosphates of sodium and potassium in a muffin recipe. All examples used 2.58 g sodium bicarbonate and 1.7 g calcium chloride per 300 g flour. The control had 2.58 g bicarbonate and 3.52 g SAPP. The results are set out in the following Table XXI, in which all weights are g per 300 g flour.

TABLE-US-00023 TABLE XXI Example Orthophosphate pH Control 7.5 63 5.35 g DKP 8.9 64 4.36 g DSP 8.8 65 2.09 g MKP 7.6 66 1.84 g MSP 7.6

[0254] The di alkali metal salts are alkaline in the absence of the Precipitant, and do not normally react with bicarbonate. All the examples gave superior leavening compared to the control, with similar taste and colour, despite the higher pH of examples 63 and 64. Example 65 was particularly good.

EXAMPLE 67

[0255] Stoichiometric SAPP/bicarbonate with 50% molar CaCl.sub.2) system according to Table XXI was compared to a stoichiometric SAPP/bicarbonate only baking powder in a standard crumpet recipe.

TABLE-US-00024 TABLE XXI Ingredient % Sodium Bicarbonate 26.1% Wheat flour 20.0% SAPP 35.9% Calcium Chloride 18% SAPP to bicarbonate 100.4% calcium chloride to SAPP (mole ratio) 100.3% calcium chloride to SAPP (with respect to 50.1% total sequestration by SAPP)

[0256] The following results were obtained as set out in Table XXII:

TABLE-US-00025 TABLE XXII Control Example 67 Height (Average of 6) (mm) 15.7 17.8 Stack height (3) (mm) 48.8 51.9 Weight (Average of 6) (g) 53.9 55.6 pH 6.83 6.33 A.sub.w (water activity) 0.9857 0.9853

EXAMPLE 68

[0257] A similar baking powder to that of Example 67 was used with 110% calcium chloride to SAPP (55% calcium chloride to SAPP by weight/total sequestration).

TABLE-US-00026 TABLE XXIII Ingredient Percentage Sodium Bicarbonate 25.5% Wheat flour 20.0% SAPP 28 35.0% Calcium Chloride 19.5% SAPP to soda 100.2% calcium chloride to SAPP 111.4% calcium chloride to SAPP (w.r.t total 55.7% sequestration by SAPP)

[0258] Results

TABLE-US-00027 TABLE XXIV Control Example 68 Height (Average of 6) 18.7 16.3 Stack height 60.49 57.17 pH 6.4 5.5 Aw 0.9840 0.9893

[0259] A massive reduction in pH was found, despite only having 10% more calcium chloride than the second trials.

EXAMPLES 69-72

[0260] Four stoichiometric SAPP/bicarbonate systems with increasing proportions of calcium chloride as set out in Table XXIV were compared to a SAPP based baking powder in pancakes. The blend provided a thicker pancake with a reduction in width. Increasing the calcium chloride dropped the pH further at the cost of width and an increase in water activity, as shown in Table XXV.

TABLE-US-00028 TABLE XXIV Example 69 Example 70 Example 71 Example72 Component Control 50% CaCl.sub.2 60% CaCl.sub.2 65% CaCl.sub.2 70% CaCl.sub.2 SAPP 40.9% 34.1% 32.97% 32.44% 31.92% Wheat flour 19.5% 23.5% 22.72% 22.35% 22.00% Sodium bicarbonate 24.8% 23.98% 23.59% 23.21% CaCI2 17.1% 19.84% 21.15% 22.41% Potassium 32.0% bicarbonate SAPP 7.1% Oil 0.5% 0.5% 0.48% 0.48% 0.47%

TABLE-US-00029 TABLE XXV Example Control 69 70 71 72 Baking Powder on 8.86 9.18 9.33 9.49 9.65 flour weight % Thickness 43.13 48.79 46.67 45.42 45.9 (stack of 3 - mm) Width (mm) 105.3 98.0 87.6 100.2 101.2 Aw 0.9078 0.9216 0.9188 0.924 0.9229 pH 7.5 7.49 7.38 7.08 7

EXAMPLE 73

[0261] The composition of Table XXVI has been tested in a wide variety of cake recipes in which it performs well with excellent leavening.

TABLE-US-00030 TABLE XXVI With respect to % mmol 100 mmol soda Refined Sodium Bicarbonate 24.8 295.2 100.0 Calcium Chloride 17.1 154.1 52.2 SAPP 34.1 153.6 52.0 Wheat flour 23.5 Rapeseed oil 0.5 Total 100

Pancakes

[0262] In addition to the foregoing, the invention relates to pancakes traditionally made by frying a pancake batter in a broad shallow pan heated from beneath.

[0263] The term batter refers to a bakery mix comprising a starch-based flour and water, in which the volume of liquid exceeds that of solid.

[0264] Pancake batter differs from cake batters in that the water content is higher, giving a less viscous batter that, when traditionally cooked, spreads across the surface of the pan to form a thin layer. Pancake batter contains more than 30% water and typically more than 35% by weight based on the weight of batter. In addition, pancake batter usually contains less fat and sugar, based on flour, than cake batter

[0265] Pancakes may be unleavened or leavened, the latter being popular in America. The present invention is of particular value in connection with American-style, leavened pancakes.

[0266] We have now discovered that when a water soluble calcium or magnesium salt is added to pancake batter it greatly increases the viscosity of the batter, limiting its tendency to spread in the pan. This is of particular value in leavened pancakes providing a thicker lighter pancake.

[0267] Our co-pending European Patent Application No. 17737349.5, the disclosure of which is incorporated herein by reference, describes the use of calcium and magnesium salts as components of leavening systems in which they act as precipitants allowing the total or partial replacement of acidulants in the leavening system.

[0268] The aforesaid co-pending Application describes the use of the leavening systems in cake batters, but does not suggest their use in pancakes. Cake batters are relatively viscous compared to pancakes and the viscosifying effect of calcium and magnesium salts is not apparent in these recipes.

The Invention

[0269] Our invention provides a pancake batter comprising flour, at least 30% by weight of water and a viscosifier comprising from 0.001 to 10% by weight, based on the weight of the batter, of a water soluble calcium or magnesium salt.

[0270] According to a second embodiment our invention comprises a method of making pancakes, which comprises frying a batter of the invention as aforesaid.

[0271] According to a third embodiment our invention provides pancakes made by frying a batter of the invention as aforesaid.

[0272] In the following discussion of the invention, unless stated to the contrary, the disclosure of alternative values for the upper or lower limit of the permitted range of a parameter, coupled with an indication that one of said values is more highly preferred than the other, is to be construed as an implied statement that each intermediate value of said parameter, lying between the more preferred and the less preferred of said alternatives, is itself preferred to said less preferred value and also to each value lying between said less preferred value and said intermediate value.

The Viscosifier

[0273] The viscosifier is preferably a calcium salt or a mixture of calcium and magnesium salts.

[0274] Examples of suitable salts include organic salts such as salts of formic, acetic, fumaric, lactic, citric, aconitic, itaconic, citraconic, tartaric, adipic, ascorbic, malic and/or lactobionic acid, and inorganic salts such as chlorides and sulphates. Calcium chloride is generally preferred.

[0275] The viscosifier is typically present in the batter in a concentration greater than 0.01%, preferably greater than 0.05%, more preferably greater than 0.1%, most preferably greater than 0.2%, but less than 10% preferably less than 5% more preferably less than 1%, most preferably less than 0.5% by weight based on the weight of batter. Preferably the viscosifier is sufficient to provide at least 1 millimole, more preferably more than 1.5 millimoles most preferably more than 2 millimoles per 100 parts of batter, but less than 5 millimole.

[0276] The preferred particle size of the viscosifier will depend on solubility and storage stability. In the case of calcium chloride, the particle size is preferably greater than 0.5 mm, more preferably greater than 1 mm to avoid deliquescence. Smaller particle sizes may need to be protected from moisture, e.g. by keeping in a sealed container or by mixing with a hydrophobic filler, such as stearin. We prefer calcium chloride prills having a particle size less than 3 mm, more preferably less than 2 mm. Larger particles may require extended periods of mixing in order to ensure complete dissolution. Other viscosifiers, which are more stable, but less soluble than calcium chloride may require milling to ensure rapid dissolution, e.g. to less than 0.5 mm.

[0277] The viscosifier may be added to the batter separately or as a component of another ingredient such as the leavening system, e.g. by using a baking powder according to our aforesaid co-pending European Patent Application.

The Leavener

[0278] The pancakes of our invention are preferably leavened. The leavening agent most commonly used comprises an alkali metal or ammonium bicarbonate, preferably sodium or potassium bicarbonate, and a substantially stoichiometric proportion of an acidulant.

[0279] The bicarbonate is preferably milled to a particle size substantially all less than 500. Preferably, in order to avoid visible spotting in the batter, the particle size is all less than 400. To avoid impaired shelf life of the end product the particle size is more preferably all less than 250, even more preferably all less than 200, most preferably less than 150.

[0280] The D50 of the bicarbonate is preferably less than 200, more preferably less than 150, even more preferably less than 100. However, to minimise caking, and avoid excessive dust, we prefer that the D50 is greater than 35, more preferably greater than 40, even more preferably greater than 50, most preferably greater than 60.

[0281] Particularly in the case of potassium bicarbonate, we prefer bicarbonate that has been coated to inhibit caking and/or degradation by atmospheric moisture or premature interaction with the acidulant. Coatings may comprise alkaline earth metal carbonates, silicon dioxide and/or anionic surfactants, such as alkali metal or alkaline earth metal soaps. Particularly preferred are hydrophobic coatings as described in US2013202758.

[0282] The acidulant is typically a compound that, when present in a stoichiometric amount in aqueous solution, reacts with bicarbonate. The Acidulant preferably has a Neutralising Value greater than 0.5, more preferably greater than 1, even more preferably greater than 2, most preferably greater than 3. The dough rate of reaction of the acidulant is preferably less than 28, more preferably less than 20, most preferably less than 15.

[0283] The acidulant preferably has a particle size substantially all less than 400, more preferably less than 250 and most preferably at least 90% by weight less than 100. It may for example comprise sodium aluminium phosphate (SALP), sodium acid pyrophosphate (SAPP), mono sodium citrate, mono- and/or di-calcium phosphate, glucono-delta-lactone, fumaric acid, maleic acid, malic acid, succinic acid, adipic acid, citric acid, tartaric acid, citraconic acid, aconitic acid, itaconic acid, mono potassium citrate and/or tartrate and/or sodium aluminium sulphate. The preferred acidulant is SAPP.

[0284] When it is desired to use a preservative, it is generally necessary to lower the pH of the batter below 6.5 and preferably below 6 for the preservative to be effective. This requires the use of quantities of acidulant in excess of the stoichiometric amount required to react with the bicarbonate.

[0285] The acidulants in common use are not able to reduce the pH sufficiently for the preservative to be fully effective. No economically viable acid is known that is sufficiently weak to retain a useful leavening capacity into the critical stages of frying when the starch is beginning to gelatinise and also strong enough to lower the pH below 6. However, such levels are easily attained using commonly available acidulants such as SAPP in the presence of a viscosifier of the invention.

[0286] As an alternative to the commonly used stoichiometric leavening agents, we prefer to use leavening systems in which the acidulant has been wholly or partially replaced by precipitant, as described in our aforesaid co-pending European Patent Application. The precipitant may be any of the viscosifiers listed herein, and the leavening system therefore provides a convenient means to introduce the viscosifier to the batter.

[0287] The leavening system may be introduced as a component of self-raising flour. The latter may for example comprise at least 0.5% by weight of the leavening agent, preferably at least 1%, more preferably at least 2%, most preferably at least 5%.

Flour

[0288] The principal solid component of the batter is flour. This is milled starch usually derived from cereals such as wheat, rye, oats, barley, maize, millet, emmer, or rice, or from starchy tubers or tap roots. The flour may be wholemeal, refined or chlorinated. The preferred flour for American style pancakes is wheat flour.

[0289] The flour is preferably present in a proportion of more than 25%, more preferably greater than 30%, most preferably greater than 35% by weight based on the total weight of the batter, but less than 47% more preferably less than 43%, most preferably less than 40%.

Water

[0290] The principal fluid component of the batter is water. The water may be added to the batter as such or, wholly or in part, as an aqueous fluid such as milk. We prefer that the water be added substantially entirely as milk, preferably cow's milk.

[0291] The total water content of the batter is preferably at least 30%, more preferably at least 35%, most preferably at least 40% by weight based on the weight of the batter, but less than 55%, more preferably less than 50%, most preferably less than 45%.

Fats

[0292] Fats are a preferred ingredient of the batter. They comprise the triglyceride esters of one or more fatty acids, which are natural or synthetic, straight or branched chain, alkyl or alkenyl carboxylic acids having between 10 and 24 carbon atoms, such as lauric, cetic, palmitic, stearic, isostearic, oleic, linoleic, linolenic, ricinoleic, or behenic acids. As used herein fats includes all such triglycerides irrespective of their melting point.

[0293] The preferred fats are vegetable oils such as olive oil, palm oil, rapeseed oil or corn oil and mixtures thereof. The fats may also comprise whale oil and/or animal fats such as butter, ghee or lard.

[0294] Pancakes normally contain at least 5% of fats based on the weight of flour. The batter preferably contains at least 2.5%, more preferably at least 3%, still more preferably at least 3.5%, most preferably at least 4% by weight of fats, based on the weight of batter, but less than 10%, more preferably less than 8%, even more preferably, less than 6%, most preferably less than 5%. This is less than cake batter, which normally contains more than 10% by weight of fat.

Other Ingredients

[0295] Pancakes normally contain at least 10% sugar based on flour weight. We prefer that our batter contains at least 1%, more preferably at least 2% by weight of sugar based on the weight of batter, but less than 10%, more preferably less than 5%, most preferably less than 3%. This is substantially less than most cake recipes.

[0296] Our batter may contain salt to taste, egg, in proportions up to about 15% based on the weight of batter, as well as any of the ingredients commonly included in pancake batter, such as flavorings, emulsifiers, gums such as xanthan gum, acidity regulators, preservatives including sorbic acid, potassium sorbate, calcium sorbate, sulphur dioxide, sodium sulphite, sodium bisulphite, sodium or potassium metabisulphite, potassium hydrogen sulphite, calcium sulphite, propionic acid, or sodium, potassium or calcium propionate, in effective proportions.

Frying

[0297] The batter is preferably fried in a frying pan, griddle or other flat metal surface heated from beneath, for example by a gas, electric or induction hob, or paraffin stove, or by combustion of solid fuel, preferably at a temperature greater than 150 C., more preferably greater than 160 C., most preferably greater than 170 C., but preferably below 200 C., more preferably below 190 C., most preferably below 180 C.

EXAMPLE

[0298] A pancake batter was made up in accordance with the recipe shown in the following table in which all proportions are percentage by weight, based on the total weight of the batter unless stated to the contrary. After standing for five minutes the mixture was fried for 90 seconds on a griddle at 177 C. to make four pancakes, which were stacked. The height of the stack was measured and compared with a control without calcium chloride.

TABLE-US-00031 TABLE Control Example Sugar 2.4 2.4 Salt 0.3 0.3 Wheat flour 37.3 37.3 Vegetable oil 4.6 4.6 Egg 11.7 11.7 Milk 42.0 42.0 Sodium bicarbonate 0.72 0.72 SAPP 28 0.98 0.15 SAPP 10 0.83 Calcium chloride 0.27 Stack height (mm) 58.35 69.22 Bake loss 11.9 6.2